JP3014318B2 - Shrink-proof wool fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shrink-proof wool fiber which imparts a shrink-proof property to wool fiber.

[0002]

2. Description of the Related Art As shown in FIG. 1, a wool fiber has a cortex 1 covered with scale-like cuticle cells 10, and an intercellular filler 2 is filled between the cuticle cells 10 and the cortex 1. The structure has been. Then, the cuticle cell 10 has a hydrophobic epicuticle layer 11.
And a hydrophilic octicle layer 12, and an endocicle layer 13 having a higher hydrophilicity than the octicle layer 12.

Here, when such wool fibers absorb water, the endocicle layer 13 on the cortex 1 side of the cuticle cell 10 and the exocuticle layer 12 on it
Swell. When the wool fibers absorb water in this manner, the endocicle layer 13 on the cortex 1 side is higher in hydrophilicity than the exotic layer 12 on the cortex 1 side, and thus the endocicle layer 13 is larger than the exotic layer 12 on it. As shown in FIG. 2, the cuticle cells 10 swell and become bent outward on the surface of the cortex 1 by the bimetal action, and the wool fibers are entangled and contracted by the warped cuticle cells 10. There was a problem.

Therefore, conventionally, in order to suppress the shrinkage due to the entanglement between the wool fibers as described above, the wool fibers have been subjected to chlorine-oxidation and shrink-proof processing.
Conventional methods for shrink-proofing wool fibers by oxidizing them with chlorine include PadAcid-DCCA processing, Split Pad method, Deep-In method, and Woo.
Shrink-proof processing methods such as lcomber's SRW processing method and continuous hypochlorous acid method have been used.

[0005] Here, these shrink-preventing methods differ in the chlorine chemical used, the pH at the time of processing, the processing machine, and the like.
By damaging or dissolving the epicuticle layer 11 and the exotactic layer 12 of the wool fiber, the bimetal effect in the cuticle cell 10 is suppressed to prevent shrinkage due to entanglement between the wool fibers. Alternatively, the cuticle layer 10 is almost completely dissolved and removed, so that the entanglement phenomenon of the cuticle layer 10 is prevented. After treating the cuticle cells 10 of the wool fiber by chlorinating the wool fiber as described above, the wool fiber is desalted and washed, and then, if necessary, an organic epichlorohydrin resin containing chlorine. And a softening treatment, followed by drying or quenching.

[0006]

However, by performing a resin treatment with an organic epichlorohydrin resin containing only chlorinated or chlorinated + chlorine, the bimetal effect in the cuticle cell 10 is suppressed or the entanglement phenomenon is prevented to prevent wool. Completely prevent felting of the fiber,
If the amount of shrinkage is to be suppressed to a practical range, there is a problem that the absorbable organic halogen flows out into the wastewater and affects fish and eventually the human body. Absorbable organic halogens that can be emitted have already been regulated by law in Germany and other countries.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a shrink-proof wool fiber which suppresses the amount of shrinkage of wool fibrous to a practical range and has less pollution problem during production. It is.

[0008]

According to the first aspect of the present invention, there is provided a wool fiber in which at least a part of cystine bonds of an octicle layer of a wool fiber is removed and wool is removed. The endecticle layer on the surface of the fiber is hydrophobized by a hydrophobizing agent, and the invention according to claim 2 is characterized in that at least a part of the cystine bond of the exocuticle layer on the surface of the wool fiber is removed. The endocicle layer on the surface of wool fiber is made hydrophobic by a reaction with a hydrophobic substance, and the invention according to claim 3 of the present invention relates to one of the cystine bonds of the exocuticle layer on the surface of wool fiber. The part is removed, and the surface of the wool fiber is hydrophobized by graft polymerization, and the invention according to claim 4 of the present invention is characterized in that: With at least a portion of the cystine bond Ekisokuchikuru layer on the surface of the hair fibers are removed, Endokuchikuru layer on the surface of the wool fibers, characterized in that formed by reaction with the keratin protein.

Next, the present invention will be described in detail.

The wool fibers referred to in the present invention include various forms such as slivers, roses, yarns, woven fabrics and knitted fabrics formed by wool fibers.

The shrink-proof wool fiber of the present invention can be produced by treating in the following steps (1) and (2), (2) and (3), or (2) and (4).

(1) Treatment of Endocicle Layer of Wool Fiber with Hydrophobizing Agent Treatment of wool fiber with a hydrophobizing agent reduces the degree of swelling of the endocicle layer. As a result, the degree of hydrophilicity of the exo-cuticle layer and the end-cuticle layer becomes closer to each other, and the bimetal effect can be suppressed in combination with the effect of modifying the surface of the wool fiber described below. Examples of the method for treating with the above-mentioned hydrophobic treating agent include formaldehyde, glyoxal, pyrogal / formaldehyde, potassium dichromate, mercuric acetate, diaminohexane / formaldehyde, and isocyanates (for example, hexamethylene diisocyte).
anate, bis (β-isocyanotoety
l) a method of introducing cross-linking into the endocicle layer by disulfide) or the like, a method of esterification with methanol / hydrochloric acid, concentrated sulfuric acid / alcohol, etc., various acid anhydrides, Sandospace S (manufactured by Sando Co., Ltd.), Sandospace R (sandwich) Company),
2,4-dichloro-s-triazin-6
For example, a method of introducing a hydrophobic bulky group into an endicle layer using various dichlorotriazine derivatives such as yl-aniline and the like can be mentioned.

(2) Modification of wool fiber surface The wool fiber is subjected to an oxidizing treatment with an oxidizing agent, a reducing treatment with a reducing agent, a low-temperature plasma or corona treatment, and then an oxidizing treatment with an oxidizing agent or a reducing treatment with a reducing agent. In addition, an anion and / or a cation are generated on the surface of wool fiber to impart hydrophilicity. That is, the outermost epicuticle layer of the surface cuticle cells of the wool fiber is damaged or eluted and removed to remove the water repellency of the wool fiber surface, and further damages the intermediate exocuticle layer, that is, the exocuticle layer. At least a part of the cystine (SS) bond is removed to generate anions and cations on the surface of the wool fiber, and the surface is made as hydrophilic as the innermost layer, ie, the endocicle layer. Usually, the exo-cuticle layer is less hydrophilic than the end-cuticle layer, and the bimetallic action resulting from this difference causes the cuticle layer to curl up in water, causing the fibers to become entangled, thereby causing a felting phenomenon. Therefore, when the hydrophilicity of both layers is made equal to each other as described above, the felting is eliminated and the wettability of the fiber surface is greatly improved.

The above oxidizing agents include hypochlorous acid (HOCl), potassium permanganate (KMnO ₅ ), sodium hydrogen persulfate (NaHSO ₅ ), potassium hydrogen persulfate (KHSO ₅ ), potassium bromate ( KBrO ₃ ), sodium hypochlorite (NaOCl) and the like can be applied. Further, as the reducing agent, sodium bisulfite (N
aHSO ₃ ), sulfurous acid (H ₂ SO ₃ ), sodium pyrosulfite (Na ₂ S ₂ O ₅ ) and the like can be applied.

The low-temperature plasma treatment is preferably performed under the following conditions. (1) Gas: oxygen, nitrogen or argon (2) Pressure: 1 torr or less (3) High frequency output: 300 W (4) Processing time: about 3 minutes

Further, as the corona treatment, a treatment preferably carried out under the following conditions may be mentioned. (1) Gas: Atmosphere (2) Frequency: 10 to 40 KHz (3) Output: 0.1 to 3 KW (4) Corona dose: 100 to 300 W · min / cm
^Two

Here, when low-temperature plasma treatment and corona treatment are applied to the wool fiber, the epicuticle layer and the exocuticle layer on the surface of the wool fiber become hydrophilic.

The chemical change of the wool fiber surface caused by the oxidizing treatment with the oxidizing agent will be described.

Oxidation of cystine

[0020]

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Cleavage of peptide bond

[0022]

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Cystine degradation by sulfite

[0024]

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Further, by introducing an ionic group by aminoethylation, carboxymethylation or the like after oxidation treatment with an oxidizing agent or reduction treatment with a reducing agent, the hydrophilicity of the exocuticle layer can be further enhanced.

The order in which the processes (1) and (2) are combined and processed is not particularly limited, and the order of the process (1) → the process (2) and the sequence of the process (2) → the process (1). Either is acceptable.

(3) Treatment of Wool Fiber by Graft Polymerization with Hydrophobic Substance Wool fiber is subjected to a graft polymerization treatment with a hydrophobic compound to reduce the degree of swelling of the whole wool fiber. This makes it difficult for the exo-cuticle layer and the end-cuticle layer to swell, and the bimetal effect can be completely suppressed in combination with the above-described effect of modifying the wool fiber surface.
As a method of performing the graft polymerization treatment with the above-mentioned hydrophobic substance, a conventionally used monomer is graft-polymerized to a wool graft such as methyl acrylate, methyl methacrylate, styrene, acrylonitrile, and acrolein using an appropriate catalyst. And graft polymerization of casein, collagen, wool protein, and silk protein using diepoxide and the like as a crosslinking agent.

The order of processing when the steps (2) and (3) are combined is as follows: step (2) → step (3).

(4) Treatment of Wool Fiber with Keratin Protein Wool fiber is treated with keratin protein to reduce the degree of swelling of the whole wool fiber. This makes it difficult for the exo-cuticle layer and the end-cuticle layer to swell, and the bimetal effect can be completely suppressed in combination with the above-described effect of modifying the wool fiber surface. The keratin proteins include wool, hair, feathers, and the like. Since these keratin proteins contain cystine bonds and are insoluble in water and all neutral solvents, they are reduced with an oxidizing agent such as hydrogen peracetate, an alkali agent such as sodium sulfide, and a reducing agent such as thioglycolic acid. Then, after breaking the SS bond or polypeptide bond to make it water-soluble, it is adsorbed to wool and then oxidized to crosslink to wool.

The order of processing when the steps (2) and (4) are combined is as follows: step (2) → step (4).

[0031]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which show that the shrink-proof wool fibers of this example are superior to the shrink-proof wool fibers of the Comparative Examples.

Example 1 First, a wool sliver having an average fineness of 21 μm was treated with a hydrophobizing agent under the following conditions. Hydrophobizing agent: formaldehyde (HCHO) 10% owf PH: 5 Treatment temperature, time: 50 ° C. × 30 minutes Bath ratio: 1:10 Next, the wool sliver subjected to the hydrophobic treatment is chlorinated under the following conditions. Was given. Effective chlorine content: 0.5% owf Processing machine: Miller-type continuous chlorination equipment Processing temperature, time: 10 ° C. × 10 seconds Next, from the wool sliver, by the usual worsted spinning process, the 48th count (meter count) Yarn was obtained. However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, using the above-mentioned yarn, the knitted fabric was knitted at a cover factor of 0.41 to form a knitted sheet.

(Comparative Example 1) The same treatment as in Example 1 was performed except that the chlorine oxidation treatment was not performed.
A knit sheet of Comparative Example 1 was obtained.

(Comparative Example 2) A knit fabric of Comparative Example 2 was obtained by performing the same treatment as in Example 1 except that the hydrophobic treatment was not performed.

(Comparative Example 3) A knit sheet of Comparative Example 3 was obtained by performing the same treatment as in Example 1 except that the hydrophobic treatment and the chlorine oxidation treatment were not performed.

The area shrinkage of these examples and comparative examples after 10 times of practical washing was measured. The results are shown in Table 1 below.

[0037]

[Table 1]

From the above results, the product of Example has an excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

Example 2 First, a wool sliver having an average fineness of 21 μm was treated with a hydrophobizing agent under the following conditions. Hydrophobizing agent: bis (β-isocyanotoety
l) disulfide 45g / l Treatment machine: Continuous sliver treatment machine (pad with 100% squeezing) Steaming heat treatment: 100 ° C. × 60 minutes after padding Next, the wool sliver subjected to the hydrophobic treatment is subjected to chlorination treatment under the following conditions. gave. Effective chlorine amount: 1% owf Processing machine: Miller-type continuous chlorination equipment Processing temperature, time: 10 ° C x 10 seconds Next, the wool sliver is used to make a 48-count (m-count) yarn by the usual worsted spinning process. Obtained. However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, using the above-mentioned yarn, the knitted fabric was knitted at a cover factor of 0.41 to form a knitted sheet.

(Comparative Example 4) The same processing as in Example 2 was performed, except that the chlorine oxidation treatment was not performed.
A knit sheet of Comparative Example 4 was obtained.

Comparative Example 5 A knit sheet of Comparative Example 5 was obtained in the same manner as in Example 2, except that the hydrophobic treatment was not performed.

(Comparative Example 6) A knit sheet of Comparative Example 6 was obtained by performing the same treatment as in Example 2 except that the hydrophobic treatment and the chlorine oxidation treatment were not performed.

The area shrinkage of these examples and comparative examples after 10 washes was measured. The results are shown in Table 2 below.

[0044]

[Table 2]

From the above results, the products of Examples have excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

Example 3 First, a wool sliver having an average fineness of 21 μm was treated with a hydrophobizing agent under the following conditions. Hydrophobizing agent: 2,4-dichloro-s-triaz
in-6-yl-pn-butyl aniline
150 g / l Treatment machine: Continuous sliver treatment machine (pad with 100% squeezing) Steam treatment: 100 ° C. × 60 minutes after the pad Next, the wool sliver subjected to the hydrophobic treatment was subjected to oxidation treatment under the following conditions. Oxidizing agent: KHSO ₅ 50 g / l (pH 7) Processing machine: Miller continuous chlorination equipment Processing temperature, time: 10 ° C. × 10 seconds Deoxygenation: NaHSO ₃ Then, the above-mentioned wool sliver is used in a usual worsted spinning process. Forty-eight (metric) yarn was obtained. However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, the above-mentioned yarn was knitted with a cover factor of 0.41 to form a knitted sheet.

(Comparative Example 7) A knit fabric of Comparative Example 7 was obtained by performing the same treatment as in Example 3 except that the oxidation treatment was not performed.

(Comparative Example 8) A knit fabric of Comparative Example 8 was obtained by performing the same treatment as in Example 3 except that the hydrophobic treatment was not performed.

(Comparative Example 9) A knit fabric of Comparative Example 9 was obtained by performing the same treatment as in Example 3 except that the hydrophobic treatment and the oxidation treatment were not performed.

The area shrinkage of these examples and comparative examples after 10 washes was measured. Table 3 shows the results.

[0051]

[Table 3]

From the above results, the products of Examples have excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

Example 4 First, a wool sliver having an average fineness of 21 μm was subjected to a chlorine oxidation treatment under the following conditions. Effective chlorine content: 0.5% owf Processing machine: Miller continuous chlorination equipment Processing temperature, time: 10 ° C. × 10 seconds Next, a wool sliver that has been subjected to chlorination treatment is treated with a hydrophobic substance under the following conditions. To give a graft treatment. Monomer: Methyl methacrylate 10% owf Catalyst: Ferrous ion / H ₂ O ₂ redox catalyst Treatment temperature, time: 50 ° C. × 1 hour Bath ratio: 1:10 Next, ordinary worsted spinning from the above-mentioned wool sliver Through the process, a yarn of count 48 was obtained. However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, the above-mentioned yarn was knitted with a cover factor of 0.41 to form a knitted sheet.

(Comparative Example 10) A knit fabric of Comparative Example 10 was obtained by performing the same treatment as in Example 4 except that the grafting treatment was not performed.

(Comparative Example 11) A knit fabric of Comparative Example 11 was obtained by performing the same treatment as in Example 4 except that the chlorine oxidation treatment and the grafting treatment were not performed.

The area shrinkage of these examples and comparative examples after 10 washes was measured. Table 4 shows the results.

[0057]

[Table 4]

From the above results, the products of Examples have excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

Example 5 First, a wool sliver having an average fineness of 21 μm was subjected to a chlorine oxidation treatment under the following conditions. Effective chlorine amount: 1.0% owf Processing machine: Miller-type continuous chlorination equipment Processing temperature, time: 10 ° C. × 10 seconds Next, a wool sliver subjected to chlorination treatment is treated with a hydrophobic substance under the following conditions. To give a graft treatment. Monomer: acrylonitrile 50 g / l Catalyst: CuSO ₄ 2.5 g / l, K ₂ S ₂ O ₈
3.0 g / l pH: 7 Treatment machine: Continuous sliver treatment machine (pad with 100% squeezing) Steaming heat treatment: 100 ° C. × 60 minutes after padding Next, the wool sliver is 48th (meter) by a usual carding spinning process. ) Was obtained. However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, the above-mentioned yarn was knitted with a cover factor of 0.41 to form a knitted sheet.

Comparative Example 12 The procedure of Example 5 was repeated, except that the grafting was not performed, to obtain a knitted fabric of Comparative Example 12.

Comparative Example 13 A knit fabric of Comparative Example 13 was obtained by performing the same treatment as in Example 5 except that the chlorine oxidation treatment and the grafting treatment were not performed.

The area shrinkage of these examples and comparative examples after 10 washes was measured. Table 5 shows the results.

[0063]

[Table 5]

From the above results, the products of Examples have excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

Example 6 First, a wool sliver having an average fineness of 21 μm was subjected to a chlorine oxidation treatment under the following conditions. Effective chlorine amount: 1.0% owf Processing machine: Miller-type continuous chlorinator Processing temperature, time: 10 ° C. × 10 seconds Next, reduced wool protein is subjected to chlorinated wool sliver under the following conditions. Granted. Application of reduced wool protein: Applied by pad nip so as to obtain 5% owf by thioglycolic acid treatment. Oxidation treatment: Next, 25 g / l of hydrogen peroxide (35%)
(PH was adjusted to 8 to 9 with soda ash) using a pad nip. Drying treatment: drying with hot air at a temperature of 80 ° C. or less The reduced wool protein was produced as follows. Wool 10
g of urea 8M, Tris-HCl 0.01M, EDTA2Na
Swelled in 500 ml of a 0.001 M aqueous solution. Next, 6m of thioglycolic acid (mercaptoethanol)
1, 5N sodium hydroxide to pH 10.3
It was kept at 0 ° C. for 2 hours. Next, after cooling to 25 ° C, 6N hydrochloric acid was added to adjust the pH to 8.5 to 9.0, and 16.08 g of monoiodoacetic acid was added thereto, followed by keeping at 25 ° C for 24 hours. Finally, this was filtered, and the filtrate was further dialyzed to remove one having a molecular weight of 35 or less.
Used as 0% drug. Next, the wool sliver was subjected to a normal worsted spinning process to obtain a yarn of count 48 (meter count). However, the number of twists of this yarn was Z 300 T / m for the top twist and Z 500 T / m for the bottom twist. Then, the above-mentioned yarn was knitted with a cover factor of 0.41 to form a knitted sheet.

Comparative Example 14 A knit fabric of Comparative Example 14 was obtained by performing the same treatment as in Example 6 except that the reduced wool protein treatment was not performed.

Comparative Example 15 Example 6 was repeated except that the chlorine oxidation treatment and the reduced wool protein treatment were not performed.
In the same manner as in the above, a knit sheet of Comparative Example 15 was obtained.

The area shrinkage of these examples and comparative examples after 10 washes was measured.

[0069]

[Table 6]

From the above results, the products of Examples have excellent washing shrinkage. On the other hand, it can be seen that the comparative example product is inferior in the washing shrinkage rate.

[0071]

As described above in detail, the shrink-proof wool fiber of the present invention is one in which the shrinkage of the wool fiber is suppressed to a practical range. It is very useful because it can be used for a wide range of applications. Further, since chlorine used can be reduced, it is very useful in environmental hygiene.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing the state of cuticle cells on the cortex surface of a wool fiber when the wool fiber does not absorb water.

FIG. 2 is an explanatory diagram showing a state of cuticle cells on the cortex surface of the wool fiber when the wool fiber absorbs water.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cortex 2 Intercellular packing 10 Cuticle cell 11 Epicuticle layer 12 Exocticle layer 13 Endocicle layer

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁷ Identification code FI D06M 101: 12 D06M 3/10 Z

Claims (4)

(57) [Claims] At least a part of cystine bonds of an exotactic layer on a surface of wool fiber is removed,
An anti-shrink wool fiber, wherein the endcuticle layer on the surface of the wool fiber is hydrophobized by a hydrophobizing agent. 2. The method according to claim 1, wherein at least a part of the cystine bond in the exotactic layer on the surface of the wool fiber is removed.
An anti-shrink wool fiber characterized in that an endocicle layer on the surface of wool fiber is hydrophobized by reaction with a hydrophobic substance. 3. The method according to claim 1, wherein at least a part of the cystine bond of the exocticle layer on the surface of the wool fiber is removed.
An anti-shrink wool fiber, wherein the surface of the wool fiber is made hydrophobic by graft polymerization. 4. The method according to claim 1, wherein at least a part of the cystine bond of the exotactic layer on the surface of the wool fiber is removed.
An anti-shrink wool fiber characterized in that an endocicle layer on the surface of wool fiber is reacted with keratin protein.